Mobility of Spin Probes in Quaternized Poly(4-vinylpyridine) Membranes

The mobility of nonionic and anionic spin probes in water-containing quaternized poly(4-vinylpyridine) membranes was investigated by means of an electron spin resonance (ESR) technique.

Poly(4-vinylpyridine) was quaternized and crosslinked by dibromoalkane Br(CH2)nBr (n=4, 6, 8, 10), and the effects of the side alkyl chain length were studied. Three spin probes,

2,2,4,4-tetramethyl-1,2,3,4-tetrahydro-γ-carboline-3-oxyl (SPII), 2,2,6,6-tetramethyl-1-piperidinyloxy (SPIV), and sodium 2,2,5,5-tetramethyl-1-pyrrolidinyloxy-3-carboxylate (ASPI), were

used. In the temperature region examined, the side methylene chain length had no effect on the mobility of SPII and SPIV, but a little effect for ASPI. This suggests that the ASPI can

monitor the mobility of the side alkyl chain. In addition, the effects of water on the mobility of the spin probes were investigated. The mobility of the spin probes was much greater in the

membrane containing 30 wt% water than in that containing 3 wt% water, and the polarity around the probes was larger in the former than in the latter membrane. From this, as pointed out in

our previous papers on nylon 6/spin probe systems, the effects of water are divided into (1) the effects on the mobilities of the polymer chains and probe molecules, and (2) the effects on

the microenvironment around the spin probes.

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